NOTES
1970
VOL. 31
TABLE I VALUESOF PERCENTSULFURICACIDAT WHICHTHE ALCOHOLOR ETHERIS HALF-PROTONATED % HISO(
.4loohols
Primary Methanol 1-Butanol 8-Phenyloctanol Secondary 2-Propanol 2-Butanol 11-Phenyl-2-undecanol Tertiary 2-Methyl-2-propanol (t-butyl)
pKa
Method and ref
41 39.5 41
-2.5 -2.3 -2.5
Raman spectrab Distributionc Solubility
(50) 36.5 39
-2.2 -2.3
Interpretation of kinetic& Distributionc Solubility
41.5 55 f 5 38.5 41
-2.6
Distributionc Interpretation of kinetics* Distribution" Solubility
2-Methyl-2-butanol -2.3 2-Methyl-1 l.-phenyl-2-undecanol -2.5 Ethers Dimethyl 54 -3.83 Distributionb Diethyl 52 -3.59 Distribution' Methyl butyl 52 -3.50 Distribution' Methyl 4-phenylbutyl 49 -3.2 Solubility Calculated from the equation, Ho = p K log (CB/CBH+), using the values of HOtabulated by M. A. Paul and F. A. Long, Chem. Rev., 57,1 (1957). b N. Den0 and M. J. Wisotsky, J . Am. Chem. SOC.,85, 1735 (1963). d P. D. Bartlett and J. 0. McCollum, ibid., 78, 1441 (1956). 6 N. Deno, T. Edwards, and C. Perizzolo, ibid., 79,2108 (1957). f See ref 2.
+
(1
4-Phenyl-1-butanol and its corresponding secondary and tertiary alcohols were studied. The results were erratic and although we suspect cyclization to tetralin derivatives, this was not verified.
Acknowledgment.-Support from the Petroleum Research Fund of the American Chemical Society is gratefully acknowledged.
Experimental Section
Bitriptycyl'
SolubilityDeterminations.-A mixture of 150 ml of the aqueous acid and 0.2 g of the alcohol or ether were swirled until an aliquot of the solution gave a constant extinction at A,, (260-270 mp). Preparation of Compounds.-The route to 8-phenyloctanol was as follows. Suberic acid was converted to the anhydride by refluxing with acetic anhydride. Excess acetic acid and anhydride were removed by distillation and the suberic anhydride condensed with benzene using aluminum chloride. This is the method of Hill,5 who reported a yield of 7-benzoylheptanoic acid of 78%. We obtained 65%. This acid was reduced to crude 8-phenyloctanoic acid in 80% yield by reduction with amalgamated zinc and hydrochloric acid using the Clemmenson conditions .e Reduction of the crude acid with LiAlHa in ether gave a 56% yield of 8-phenyl-1-octanol, bp 146-147' (2.5 mm). A n d . Calcd for C14H220: C, 81.5; H, 10.8. Found: C, 81.5; H, 10.9. 10-Phenyldecanoic acid, bp 224225' (14 mm), was prepared in a manner identical with the preparation of 8-phenyloctanoic acid, but using decanedioic acid in place of octanedioic (suberic) acid. The acid chloride, bp 180-184' (12 mm), was prepared by refluxing the acid with thionyl chloride and a trace of pyridine. The acid chloride was treated with dimethylcadmium by the method of Cason' to produce ll-phenyl-2-undecanone, bp 137139" (3 mm), in 40% yield. A LiAlHd reduction in ether converted the ketone quantitatively to 11-phenyl-2-undecanol, bp 133-134' (13 mm). A n d . Calcd for C1&0: C, 82.2; H, 11.4. Found: C, 82.0; H, 11.6. Treatment of 11-phenyl-2-undecanone with excess CHaMgI quantitatively produced 2-methyl-ll-phenyl-2-undecanol,bp 130-131" (7 mm). Anal. Calcd for C18H8~O:C, 82.4; H, 11.5. Found: C, 82.0; H, 11.6. Methvl 4-uhenvlbutvl ether was preuared by the reaction of Cphenyi-1-bbtanol wiih potassium m&al in eiher followed by addition of exceas iodomethane. The boiling point of the ether, 108-109' (11 mm), was in accord with the literature.8 (5) J. W. Hill, J . A m . Chem. Soc., 64, 4105 (1932). (6) E. L. Martin, O w . Reactions, 1, 155 (1942). (7) J. Cason, Chem. Rev.,40, 15 (1947). (8) J. von Braun, Rsr., 44, 2871 (1911).
CONSTANTINE KOUKOTAS, STANLEY P. MEHLMAN, AND LEONARD H. SCHWARTZ~ Department of Chemistry, The City College of the City University of New York, New York, New York 10081 Received November 19,1965
While numerous experiments conducted over the past fifteen years could have been expected to yield bitriptycyl (I), this hydrocarbon has yet to be unequivocally described. Thus, coupling fails to take place when 9-bromotriptycene is heated with copper, zinc, or s i l ~ e r . ~ 1Similarly, 4 bitriptycyl has not been reported among the products resulting from the reaction of 9-triptycyllithium with cobalt chloride, copper chloride, or nickel chloride, or the silver-catalyzed thermal decomposition of 9,9'-ditriptycylmercury, or the copper- or silver-catalyzed thermal decomposition of 9,9'-ditriptycyldiselenide.4 Bartlett and Greene,s in the course of studying the thermal decomposition of ditriptoyl peroxide, isolated a small amount of a high-melting solid, "compound x," which they suggested might be bitriptycyl. We now wish to report a synthesis of bitriptycyl, to describe the properties of this hydrocarbon, and (1) This work waa supported in part by grants from the National Science Foundation (GP3511), the Research Corporation, and the General Faculty Research Committee of the City College of New York. The purchase of the Cary Model 14 spectrophotometer used in this work was made possible by a grant from the National Science Foundation (GP-3646) to the City College of the City University of New York. (2) To whom inquiries should be addrewed. (3) P. D. Bartlett and E. S. Lewis, J . A m . Chem. Soc., 74, 1005 (1950). (4) G. Wittig and W. Toohtermann, Ann. Chem., 660, 23 (1962). (5) P. D. Bartlett and F. D. Greene, J . A m . Chem. SOC.,76, 1088 (19.54).
NOTES
JUNE 1966 4’
6’
20
4
I further, to confirm the structure assignment made by Bartlett and Greene for their “compound x.” The present synthesis of bitriptycyl involves the addition of benzyne to 9,9’-bianthryl. For this purpose, benzyne was generated from anthranilic acid,s 1,2bromoflu~robenzene,~ and lJ2,3-benzothiadiazole 1,ldioxide.8 The yielda of bitriptycyl ranged from approximately 5-20%. The synthesis involving benzyne generated from anthranilic acid was the most convenient and generally gave the highest yields and the purest product. The isolation of bitriptycyl was considerably simplified by the extreme insolubility of this hydrocarbon in acetone. Bitriptycyl melts at 577” with decomposition, and in the absence of oxygen appears to be thermally stable up to its melting point. The proof of structure of bitryptycyl is based on the following facts. Carbon and hydrogen analysis is consistent with the formula C49Hs6. The mass spectrum shows a base peak a t m/e 506 (molecular ion), a strong peak at m/e 253 (triptycyl ion plus a double charged molecular ion) and a metastable ion at approximately m/e 127. These data serve to establish the molecular weight and also indicate that cleavage of the molecular ion to the triptycyl ion is an important process. The 280 mp (log E 3.69), ultraviolet spectrum, A:oal;&ne 272 (3.63), and 266 (sh) (3.38), compares favorably with the ultraviolet spectrum of triptycene, 279 mp (log e 3.67), 271 (3.55), and 265 (sh) (3.32). The infrared spectrum is relatively simple and agrees with the published spectrum of Bartlett and Greene’s “compoundx.” Our interest in the bitriptycyl system arises from the possibility that suitably substituted derivatives, e.g., a 2,2’-disubstituted bitriptycyl, may exhibit conformational stability. We are presently investigating this possibility. Experimental Section Infrared and ultraviolet spectra were determined on PerkinElmer Model 137 and Cary Model 14 spectrophotometers, respectively. Mass spectra were determined on an Associated Electrical Industries MS-9 spectrometer. Elemental analyses were performed by Schwarzkopf Microanalytical Laboratory, Woodside, N.Y. The melting point of bitriptycyl is uncorrected.9 Reaction of 9,9’-Bianthryland Anthranilic Acid and n-Butyl Nitrite.-Solutions of anthranilic acid (4.12 g, 30 mmoles) and n-butyl nitrite (3.49 g, 34 mmoles), each in 27 ml of 2-butanone, were simultaneously added during a 3.5-hr period to a stirred (6) L. Friedman and F. M. Logullo, J . Am. Chem. SOC.,86,1549 (1963). (7) G.Wittig and L. Pohmer, Chem. Ber., 89, 1334 (1956). (8) G.Wittig and R. W. Hoffmann, ibid., 96, 2718 (1962). (9) The melting point of bitriptycyl was determined in a sealed tube, under nitrogen, using a zinc chloride bath and a 10G-62O0 partial-immersion thermometer, supplied by the Chemical Rubber Company, Cleveland, Ohio.
1971
refluxing solution of 9,9’-bianthryl1° (0.50 g, 1.4 mmoles) in 25 ml of 2-butanone. The n-butyl nitrite solution was always in slight excess over the anthranilic acid solution. The reaction mixture was refluxed for an additional 1 hr and allowed to stand a t room temperature for a t least 12 hr in order to ensure complete precipitation of the product. The solid was filtered and repeatedly triturated with acetone. Two crystallizations from nitrobenzene gave a white solid: mp 577 f 5’ dec; yNujol 1284 (w),1151 (m), 1133 (w), 1036 (m), 915 (m) 808 (m), 771 (m), 753 (m), 745 (s), and 738 (s) cm-l; At:$ ( IO-cm cell) 280 mp (log E 3.69), 272 (3.63), and 266 (sh) (3.38); m/e 506 (base peak), mle 253 (56% of base peak), and m/e approximately 127 (metastable ion). For comparison, triptycene has ?:A: 279 mp (log E 3.67), 271 (3.55), and 265 (sh) (3.32). Anal. Calcd for C~OHZS: C, 94.83; H, 5.17. Found: C, 94.96; H, 5.15.
Acknowledgment.-The authors thank Dr. William Milne of the National Institutes of Health for the measurement and interpretation of the mass spectra. (10) F. Bell and D. H. Waring, J. Chem. Soc., 1579 (1949).
Magnetic Nonequivalence of a Thiophosphate Ester R. V. MOENAND W. H. MUELLER Analytical Research Division and Central Basic Research Laboratory, Esso Research and Engineering Company, Linden, New Jersey 7036 Received November 1.3, 1966
Magnetic nonequivalence due to molecular asymmetry has been reported for a variety of compounds.’-3 Roberts, et d J 4 studied nmr spectra of 1-phenylethyl benzyl ether and related compounds. I n particular, the effect of the proximity of an asymmetric center on the extent of magnetic nonequivalence was investigated. Sidall and Prohaska5 have observed nonequivalence of the alkoxy1 groups on a variety of phosphorus esters. This effect was explained by a preferred conformation of these esters. Bentrudeearecently - reported that
LCl8
shows magnetically nonequivalent methoxyl groups (A = 4 cps), ascribed to the asymmetric carbon in the molecule. (1) E.I. Snyder, J . Am. Chem. Soc., 86, 2624 (1963). (2) J. K. Randall, J. J. McLeskey, 111, P. Smith, and M. E. Hobbs, i b i d , , 86,3229 (1964). (3) R. M. Moriarty, J . Ow. Chem., 80,600 (1965). (4) G. M. Whiteaides, D. Holtz, and J. D. Roberts, J. Am. Chem. Soc., 86,2628 (1964). (5) T.H.Siddall and C. A. Prohaska, ibid., 84,3467 (1962). (6) (a) W.G. Bentrude, ibid., 81, 4026 (1965). (b) It was pointed o u t by a referee t h a t the nonequivalence in this compound presumably originates in a folded conformation I of higher energy than some open conformation 11, and increasing the temperature increases the population of I.
* 3-s
\
P=O
CHs
/
‘CH”
I
--+
*C=S
0-CH4Hs P ‘’
‘0 I1
